Dehydroabietic acid derivative



Patented May 18, 1943 DEHYDROABIETIC ACID DERIVATIVE Edwin E. Littmann,Westfield, N. 3., assignor to Hercules Powder Company, Wilmington, Del.,a corporation of Delaware No Drawing. Original application September 29,

1938, plication March 8 Claims.

This invention relates to new compositions of matter and methods ofproducing them. It relates more particularly to derivatives ofdehydroabietic acid and to methods for their produc tion. 1

In my co-pending application for United States Letters Patent, SerialNo. 84,877, filed June 12, 1936, which is in turn a continuation-in-partof my application for United States Letters Patent, Serial No. 6403,filed February 13, 1935, I described a process for treating rosin, rosinacids, or other compounds containing the hydrocarbon Serial No. 232,315.Divided and this ap- 14, 1941, Serial No. 383,366

Melting point a C 160-161 nucleus of a rosin acid with an active hydro-R fractive index 20 1,5371 genation catalyst, suchas nickel, copper, chospecific rotation +60 mite, platinum, palladium, etc., to produce aNeutral equivalent 299.5 change in the chemical and physical prop-Mo1ecu1ar weight 300 ertics of the rosin or rosin derivative, theresultant product having a greatly decreased unsaturation and in manycases a higher melting-point It has been identified as havingthefollowing structural formula:

and improved properties. These changes in the H O physical and chemicalcharacteristics of the ma- X terial are believed to be due to anintraand A inter-molecular rearrangement of the hydrogen I atomsoccurring therein, with no change in the VW carbon skeleton. The processconsists essentially 2 of treating the rosin, rosin acid, or compound 1CHa containing the hydrocarbon nucleus of a rosin acidwith the activehydrogenation catalyst at on cni an elevated temperature, the optimumrange being from about 150 C. to about 250 C.

Further. examination of the, product of the above treatment of rosincompounds has led to the observation that it consists of a mixture of atleast two types of chemical compounds, the major portion containing anaromatic ring, another portion being a saturated derivative of the rosincompound. I have separated from the product obtained by the treatment ofa rosin acid the major portion consisting of an acid which .I haveidentified as dehydroabietic acid, inasmuch as it appears to contain twoless hydrogen atoms than abietic acid, contains one aromatic ring, andhas the known physical constants of dehydroabietic acid as described inthe literature. The dehydroabietic acid may be separated from thetreated rosin by various means, crystallization from a solvent solutionbeing a practical method.

Thus, by way of example, to 125 parts by weight of the product of thetreatment of 1 wood rosin with a palladium catalyst under the conditionsdescribed in the application, Serial No. 84,877, filed June 12, 1936,are added 170 parts by weight oracetone. ,After heating to efiectsolution the product is cooled and the crystals separating are Othermethods of preparing dehydroabietic acid have been described in theliterature and the above structural formula has been accepted asrepresenting the structure of the acid. However, some question existsconcerning thev exact location of the methyl and isopropyl groups. Forthe purpose of defining this invention these groups are located asshown.

In my co-pending application,- Serial, No. 226,573, filed August 24,19.38, I have described derivatives of dehydroabietic acidinvolvingsubstitution in the carboxyl group. The derivatives are esters,salts, acyl halides, amines, ethers, primary alcohol, etc., whichcontain the hydrocarbon nucleus of dehydroabietic acid.

Now, in accordance with the present invention, I may prepare amino orsubstituted amino derivatives of dehydroabietic acid itself or compoundscontaining the hydrocarbon nucleus of dehydroabietic acid, in which theamino or substituted amino groups are in the aromatic ring of thehydrocarbon nucleus of dehydroabietic acid. Thus, in general, thederivatives which I may prepare in accordance with this' 'invention willbe amino or substituted amino derivatives of dehydroabietic acid itselfor of esters, salts, acyl halides, amides, ethers, primary alcohols,etc., derived from dehydroabietic acid and containing the hydrocarbonnucleus of dehydroabietic acid.

As a general expression of my invention, the derivatives which I mayprepare are expressed by the following general formula:

wherein A is a bivalent element or group such as O, S, H2, NX, etc.,where X is hydrogen or a monovalent organic radical; R is a monovalentelement or group such as OH, SH, O-metal, O-NH4, halogen, OX, SX, NXX,etc., where X is hydrogen or a monovalent organic radical; a and/or 1)and/or are monovalent elements or groups such as H, NH2 and NXz where X2is a divalent organic radical, two monovalent organic radicals, orhydrogen and a monovalent organic radical. No more than two of thesubstituents a, b and c may be hydrogen within the scope of thisinvention.

Thus, in general, the derivatives of dehydroabietic acid which I mayprepare in accordance with this invention, may or may not be substitutedin the carboxyl group and will be acids, esters, salts, acyl halides,amides, ethers, primary alcohols, etc., and will be substituted in thearomatic nucleus of the dehydroabietic acid, or compound containing thehydrocarbon nucleus of dehydroabietic acid, in one or more of the threepossible positions with substituents such as NHz and NX2, where X2 is adivalent organic radical, two monovalent organic radicals or hydrogenand a monovalent organic radical.

The amino derivatives of dehydroabietic acid itself or compoundscontaining the hydrocarbon nucleus of dehydroabietic acid may beprepared from the corresponding nitro derivatives by the usual reductionmethods. The amino derivative produced may then be treated to obtainsubstituted amino derivatives, thus, the amino derivative may bediazotized and coupled to an azo coupling agent such as, for example,R-salt, beta-naphthylamine, beta-naphthol, phenol, etc., to yield azodyestufis. hydroabietic acid in this manner have many interestingproperties which render them very attractive commercially. In reducingthe dinitro derivative to give an amino derivative, the reduction mayalso be interrupted when only one of the nitro groups has been reduced,thus, yielding a nitro amino derivative.

It is believed that substitution in the aromatic ring occurs principallyat the a and b positions, but under certain specific conditions, it maybe possible to obtain substitution at the 0 position. I am unable todesignate in exactly which position substitution is obtained for thereason that to do so would require a very extensive research into thedegradation products to give identifiable derivatives. In mostinstances, the exact location of the substituent group or groups is notof great importance, since the usefulness of the compounds would not beappreciably changed Dyes derived from dewith the three diiierentpositions of the group or groups. I am able, however, to designate thenumber of substituent groups which are introduced into the aromaticring.

Substitution in the aromatic nucleus of dehydroabietic acid or acompound containing the hydrocarbon nucleus of dehydroabietic acid bythe amino or substituted amino groups may be performed on thedehydroabietic acid itself and the acid may then be treated by any ofthe known methods to replace the carboxyl group with any of the groupsdesired, or the dehydroabietic acid may first be converted to aderivative of the acid containing the hydrocarbon nucleus ofdehydroabietic acid, and the resulting derivative treated to introducethe amino or substituted amino groups into the aromatic nucleus.

As examples illustrating the preparation of derivatives ofdehydroabietic acid in accordance with this invention, the following arecited:

EXAMPLE 1 Dinitrodehydroabietic acid To 16.5 parts by weight of 98 percent nitric acid cooled to 05 C., parts by weight of dehydroabietic acidwere added in small portions with agitation. The mixture was then pouredinto cold water and the reaction product filtered oil. The precipitatewas washed with water, dried, then crystallized from a mixture of 3parts by weight of acetone and. one part by weight of water. Therecovered product had a melting-point of l58-16l C., and a nitrogencontent of about 7.3 per cent. The nitrogencontent of the dinitroderivative is 7.2 per cent, based on the formula CzoI-IzsOsNz.

EXAMPLE 2 Methyl dinitrodehydroabietate Three parts by weight of methyldehydroabietate were added to a mixture of 5 parts by weight of 6'7 percent nitric acid and parts by weight of 95- per cent sulphuric acidgradually with good agitation. The mixture was then heated at atemperature of about it0 about C. for about five minutes. After cooling,the mixture was poured into cold water and the precipitated nitroderivative crystallized from a 1:3 mixture of acetone and methylalcohol. The yield was about 2 parts by weight of the dinitro derivativehaving a melting-point of 192-193 "C. and a nitrogen content of 6.3 percent as compared with 6.9 per cent calculated for CziI-IzaNaOs. It is aslightly yellow material crystallizing in needles.

EXAMPLE 3 Methyl dinitrodehydroabz'etate Sixteen parts by weight ofmethyl dehydroabietate were added to parts by weight of 98 per centnitric acid in small portions while maintaining the temperature at about10 t about 20 C. The reaction mixture was then poured into water, thereaction product filtered off and washed with methyl alcohol. Afterdrying the product by exposure to air it was crystallized from a 1:3mixture of acetone and methyl alco- 1101. It had the propertiesdescribed in Ex- 0 ample 2.

EXAMPLE 4 Nitroaminodehydroabietic acid EXAMPLE Methylnitroaminodehydroabietate A mixture of 100 parts by weight of aceticacid, 4.1 parts by weight ,of methyl dinitrodehydroabietate prepared asin Examples 2 and 3, and 0.1 part by weight of platinum oxide catalystwas reduced with hydrogen at room temperature.

and a pressure of about 50 lbs. per square inch. About 4 moles ofhydrogen were absorbed for each mole of methyl dinitrodehydroabietate.The solution was then warmed, the catalyst filtered oil, and thesolution poured into cold water. The precipitate was filtered oil,washed thoroughly with water, then dried. After crystallization fromslightly diluted methyl alcohol the product consisting chiefly of methylnitroaminodehydroabietate was obtained as a yellow crystalline materialhaving a melting-point of 239- 241 C.

EXAMPLE 6 Methyl diaminodehydroabietate The methyldinitrodehydroabietate prepared as in Examples 2 and 3 above was reducedwith hydrogen in methyl alcohol solution at a temperature of about 150C. and a pressure of about 2000 lbs. per square inch. The resultingdiamino derivative was crystallized from dilute methyl alcohol. It hada. melting-point of 133-134 C. On analysis it was found to have thefollowing composition:

Calculated Found for O2l 32N2OI Per cent Carbon. 72. 6 72. 80 Hydrogen9. 3 0. 24 Nitrogen 7. 7 8. 08

It is a. yellowish white powder soluble in dilute acids and is capableof being diazotized and coupled to an aromatic compound.

EXAMPLE '7 Methyl diaminodehydroabietate dibenzoate From the methyldiaminodehydroabietate produced as in Example 6 numerous derivatives inwhich the hydrogens of the NH2 groups are replaced by alkyl, aryl,aralkyl and acyl groups may be prepared.

By reacting the methyl diaminodehydroabietate with benzoyl chloride abenzoate may be prepared in which two acyl groups, namely CsHsCO-gmups,replace one of the hydrogens in each of the NH: groups.

This diamide was prepared by agitating a mix- "ture of 42 parts byweight of methyl diaminodehydroabietate prepared as in Example 6, 4.2parts by weight of benzoyl chloride'and 2 parts by weight of a 5 percent solution of sodium hydroxide, agitation being continued until themixture had cooled. The reaction product was filtered off, washed withwater and purified by reprecipitationfrom alcohol with water. The driedreaction product had a melting-point of 208 209 C. and a nitrogencontent of 5.35 per cent. Calculated for the diamide C35H40O4N2, thenitrogen content is 5.07 per cent.

The methyl diaminodehydroabietate may be diazotized and coupled to asuitable aromatic compound containing an amino, hydroxyl, or otheractivating group to produce azo dyes. A procedure for producing an azodye in this manner is as follows:

EXAMPLE 8 Diazotizatz'on of methyl diaminodehydroabietate and couplingto R-salt To 4.16 parts by weight of methyl diaminodehydroabietateprepared as in Example 6 dissolved in parts by weight of water and 3parts by weight of 3'7 per cent hydrochloric acid and cooled to about 5C. were added 1.4 parts by weight of sodium nitrite. Then 8.3 parts :byweight of R-salt were added. After thorough mixing the solution was madeslightly alkaline with 10 per cent sodium hydroxide solution. The dyewas recovered by evaporation of the solution to dryness and extractionof the dye from the salt with alcohol. The dye will dye wool a brilliantred color.

By substitution of the R-salt with beta-naphthylamine a dye is obtainedwhich will dye wool a tannish orange color.

It will be understood that the details and examples hereinbefore setforth are illustrative only, and that the invention as herein broadlydescribed and claimed is in no way limited thereby.

It will be understood also that the term dehydroabietic acid used hereinin the examples and claims refers to the particular acid known in theliterature by that name and believed to be represented by the structuralformula presented herein.

This application forms a division of my application Serial N0. 232,315,filed September 29, 1938, entitled Dehydroabietic acid derivatives, nowU. S. Patent 2,240,936, dated May 6, 1941.

What I claim and desire to protect by Letters Patent is:

AS a new o position of matter, a diazotized aminodehydroabietic acidcoupled to an aromatic coupling compound selected from the groupconsisting of benzene and naphthalene coupling compounds.

2. As a new composition of matter, a diazotized aminodehydroabietic acidcoupled to R-salt.

3. As a new composition of matter a diazotized aminodehydroabietic acidcoupled to a naphthylamine.

4. As a new composition of matter, a diazotized aminodehydroabietic acidcoupled to beta-naphthol.

5. As a new composition of matter, a diazotized material selected fromthe group consisting of diazotized amino ldehydroabietic acid anddiazotized amino dehydroabietic acid esters coupled to an aromaticcoupling compound selected from the group consisting of benzene andnaphthalene coupling compounds.

6. As a new composition of matter, a diazotized material selected fromthe group consisting of diazotized amino dehydroabietic acid anddiazotized amino dehydroa-bietic acid esters coupled 8. As a, newcomposition of matter, a. diazotized to R-salt. material selectedfrom'the group consisting of 7 As a. new composition of matter, adiazotized diazotized amino dehydroabietic acid and dia-zomaterialselected from the group consisting of tized amino dehydroa-bietic acidesters coupled to diazotized amino dehydroabietic acid and diazo- 5beta-naphthol.

tized amino dehydroabietic acid esters coupled to EDWIN R. LI'I'IMANN.

naphthylamine.

